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1.
J. F. Arambula R. McCall K. J. Sidoran D. Magda N. A. Mitchell C. W. Bielawski V. M. Lynch J. L. Sessler K. Arumugam 《Chemical science》2016,7(2):1245-1256
Ferrocene containing N-heterocyclic carbene (NHC) ligated gold(i) complexes of the type [Au(NHC)2]+ were prepared and found to be capable of regulating the formation of reactive oxygen species (ROS) via multiple mechanisms. Single crystal X-ray analysis of bis(1-(ferrocenylmethyl)-3-mesitylimidazol-2-ylidene)-gold(i) chloride (5) and bis(1,3-di(ferrocenylmethyl)imidazol-2-ylidene)-gold(i) chloride (6) revealed a quasi-linear geometry around the gold(i) centers (i.e., the C–Au–C bond angle were measured to be ∼177° and all the Au–Ccarbene bonds distances were in the range of 2.00 (7)–2.03 (1) Å). A series of cell studies indicated that cell proliferation inhibition and ROS generation were directly proportional to the amount of ferrocene contained within the [Au(NHC)2]+ complexes (IC50 of 6 < 5 < bis(1-benzyl-3-mesitylimidazol-2-ylidene)-gold(i) chloride (4)). Complexes 4–6 were also confirmed to inhibit thioredoxin reductase as inferred from lipoate reduction assays and increased chelatable intracellular zinc concentrations. RNA microarray gene expression assays revealed that 6 induces endoplasmic reticulum stress response pathways as a result of ROS increase. 相似文献
2.
Qingquan Lu Jian Zhang Pan Peng Guanghui Zhang Zhiliang Huang Hong Yi Jeffrey T. Miller Aiwen Lei 《Chemical science》2015,6(8):4851-4854
An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(ii) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(i) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(ii) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfones are synthesized with good to excellent yields under mild conditions. 相似文献
3.
Cu(i)-substituted metal oxide photocatalysts were prepared using molten CuCl treatment of wide band gap photocatalysts. The Cu(i)-substituted metal oxide photocatalysts possessed a new absorption band in the visible light region and showed photocatalytic activity for hydrogen evolution from an aqueous solution containing sulfur sacrificial reagents under visible light irradiation. Notably, the Cu(i)–K2La2Ti3O10 and Cu(i)–NaTaO3 photocatalysts showed relatively high activities for hydrogen evolution and gave apparent quantum yields of 0.18% at 420 nm. These photocatalysts responded up to 620 nm. Thus, Cu(i)-substitution using a molten CuCl treatment was an effective strategy for sensitizing a metal oxide photocatalyst with a wide band gap to visible light. 相似文献
4.
Prinson P. Samuel Roman Neufeld Kartik Chandra Mondal Herbert W. Roesky Regine Herbst-Irmer Dietmar Stalke Serhiy Demeshko Franc Meyer Vallyanga Chalil Rojisha Susmita De Pattiyil Parameswaran A. Claudia Stückl Wolfgang Kaim Jonathan H. Christian Jasleen K. Bindra Naresh S. Dalal 《Chemical science》2015,6(5):3148-3153
Cr(i)Cl is a very unstable species. The present work describes the stabilisation of Cr(i)Cl in the low coordinate environment of cyclic alkyl(amino) carbene ligands and its synthetic application to yield an unprecedented cationic complex with a two coordinate Cr(i). One electron reduction of (cAAC)2CrCl2 (1) with equivalent amount of KC8 results in the formation of (cAAC)2CrCl (2), with a distorted trigonal planar configuration at the metal centre. SQUID, EPR and theoretical studies reveal a Cr(i) centre with S = 5/2 spin ground state for 2. It represents the first example of a mononuclear Cr complex showing slow relaxation of magnetisation under an applied magnetic field. The chlorine atom in 2 is expected to be prone to further reactions with appropriate reagents. This qualifies 2 as a promising precursor for the preparation of various interesting complexes with Cr(i) in a low coordinate environment. The first example of this metathesis reaction is observed when 2 is treated with Na[B(C6H3(CF3)2)4] resulting in [(cAAC)2Cr]+[B(C6H3(CF3)2)4]–, a linear cationic complex with two coordinate Cr(i) and an S = 5/2 spin ground state. 相似文献
5.
Human S100A12 is a host-defense protein expressed and released by neutrophils that contributes to innate immunity. Apo S100A12 is a 21 kDa antiparallel homodimer that harbors two Ca(ii)-binding EF-hand domains per subunit and exhibits two His3Asp motifs for chelating transition metal ions at the homodimer interface. In this work, we present results from metal-binding studies and microbiology assays designed to ascertain whether Ca(ii) ions modulate the Zn(ii)-binding properties of S100A12 and further evaluate the antimicrobial properties of this protein. Our metal-depletion studies reveal that Ca(ii) ions enhance the ability of S100A12 to sequester Zn(ii) from microbial growth media. We report that human S100A12 has antifungal activity against Candida albicans, C. krusei, C. glabrata and C. tropicalis, all of which cause human disease. This antifungal activity is Ca(ii)-dependent and requires the His3Asp metal-binding sites. We expand upon prior studies of the antibacterial activity of S100A12 and report Ca(ii)-dependent and strain-selective behavior. S100A12 exhibits in vitro growth inhibitory activity against Listeria monocytogenes. In contrast, S100A12 has negligible effect on the growth of Escherichia coli K-12 and Pseudomonas aeruginosa PAO1. Loss of functional ZnuABC, a high-affinity Zn(ii) import system, increases the susceptibility of E. coli and P. aeruginosa to S100A12, indicating that S100A12 deprives these mutant strains of Zn(ii). To evaluate the Zn(ii)-binding sites of S100A12 in solution, we present studies using Co(ii) as a spectroscopic probe and chromophoric small-molecule chelators in Zn(ii) competition titrations. We confirm that S100A12 binds Zn(ii) with a 2 : 1 stoichiometry, and our data indicate sub-nanomolar affinity binding. Taken together, these data support a model whereby S100A12 uses Ca(ii) ions to tune its Zn(ii)-chelating properties and antimicrobial activity. 相似文献
6.
In 1953, Pauling and Corey postulated “rippled” β-sheets, composed of a mixture of d- and l-peptide strands, as a hypothetical alternative to the now well-established structures of “pleated” β-sheets, which they proposed as a component of all-l-proteins. Growing interest in rippled β-sheets over the past decade has led to the development of mixtures of d- and l-peptides for biomedical applications, and a theory has emerged that mixtures of enantiomeric β-sheet peptides prefer to co-assemble in a heterochiral fashion to form rippled β-sheets. Intrigued by conflicting reports that enantiomeric β-sheet peptides prefer to self-assemble in a homochiral fashion to form pleated β-sheets, we set out address this controversy using two β-sheet peptides derived from Aβ17–23 and Aβ30–36, peptides 1a and 1b. Each of these peptides self-assembles to form tetramers comprising sandwiches of β-sheet dimers in aqueous solution. Through solution-phase NMR spectroscopy, we characterize the different species formed when peptides 1a and 1b are mixed with their respective d-enantiomers, peptides ent-1a and ent-1b. 1H NMR, DOSY, and 1H,15N-HSQC experiments reveal that mixing peptides 1a and ent-1a results in the predominant formation of homochiral tetramers, with a smaller fraction of a new heterochiral tetramer, and mixing peptides 1b and ent-1b does not result in any detectable heterochiral assembly. 15N-edited NOESY reveals that the heterochiral tetramer formed by peptides 1a and ent-1a is composed of two homochiral dimers. Collectively, these NMR studies of Aβ-derived peptides provide compelling evidence that enantiomeric β-sheet peptides prefer to self-assemble in a homochiral fashion in aqueous solution.In aqueous solution, mixtures of l- and d- macrocyclic β-sheet peptides derived from Aβ self-assemble to form homochiral pleated β-sheets but do not co-assemble to form heterochiral rippled β-sheets. 相似文献
7.
In the presence of bidentate 1,n-bis-diphenylphosphinoalkane-CoCl2 complexes {Cl2Co[P ∼ P]} and Me3Al or methylaluminoxane, acyclic (E)-1,3-dienes react with ethylene (1 atmosphere) to give excellent yields of hydrovinylation products. The regioselectivity (1,4- or 1,2-addition) and the alkene configuration (E- or Z-) of the resulting product depend on the nature of the ligand and temperature at which the reaction is carried out. Cobalt(ii)-complexes of 1,1-diphenylphosphinomethane and similar ligands with narrow bite angles give mostly 1,2-addition, retaining the E-geometry of the original diene. Complexes of most other ligands at low temperature (–40 °C) give almost exclusively a single branched product, (Z)-3-alkylhexa-1,4-diene, which arises from a 1,4-hydrovinylation reaction. A minor product is the linear adduct, a 6-alkyl-hexa-1,4-diene, also arising from a 1,4-addition of ethylene. As the temperature is increased, a higher proportion of the major branched-1,4-adduct appears as the (E)-isomer. The unexpectedly high selectivity seen in the Co-catalysed reaction as compared to the corresponding Ni-catalysed reaction can be rationalized by invoking the intermediacy of an η4-[(diene)[P ∼ P]CoH]+-complex and its subsequent reactions. The enhanced reactivity of terminal E-1,3-dienes over the corresponding Z-dienes can also be explained on the basis of the ease of formation of this η4-complex in the former case. The lack of reactivity of the X2Co(dppb) (X = Cl, Br) complexes in the presence of Zn/ZnI2 makes the Me3Al-mediated reaction different from the previously reported hydroalkenylation of dienes. Electron-rich phospholanes, bis-oxazolines and N-heterocyclic carbenes appear to be poor ligands for the Co(ii)-catalysed hydrovinylation of 1,3-dienes. An extensive survey of chiral ligands reveals that complexes of DIOP, BDPP and Josiphos ligands are quite effective for these reactions even at –45 °C and enantioselectivities in the range of 90–99% ee can be realized for a variety of 1,3-dienes. Cobalt(ii)-complex of an electron-deficient Josiphos ligand is especially active, requiring only <1 mol% catalyst to effect the reactions. 相似文献
8.
Chao-Shen Zhang Bei-Bei Zhang Liang Zhong Xiang-Yu Chen Zhi-Xiang Wang 《Chemical science》2022,13(13):3728
A DFT study has been conducted to understand the asymmetric alkyl–alkyl bond formation through nickel-catalysed reductive coupling of racemic alkyl bromide with olefin in the presence of hydrosilane and K3PO4. The key findings of the study include: (i) under the reductive experimental conditions, the Ni(ii) precursor is easily activated/reduced to Ni(0) species which can serve as an active species to start a Ni(0)/Ni(ii) catalytic cycle. (ii) Alternatively, the reaction may proceed via a Ni(i)/Ni(ii)/Ni(iii) catalytic cycle starting with a Ni(i) species such as Ni(i)–Br. The generation of a Ni(i) active species via comproportionation of Ni(ii) and Ni(0) species is highly unlikely, because the necessary Ni(0) species is strongly stabilized by olefin. Alternatively, a cage effect enabled generation of a Ni(i) active catalyst from the Ni(ii) species involved in the Ni(0)/Ni(ii) cycle was proposed to be a viable mechanism. (iii) In both catalytic cycles, K3PO4 greatly facilitates the hydrosilane hydride transfer for reducing olefin to an alkyl coupling partner. The reduction proceeds by converting a Ni–Br bond to a Ni–H bond via hydrosilane hydride transfer to a Ni–alkyl bond via olefin insertion. On the basis of two catalytic cycles, the origins for enantioconvergence and enantioselectivity control were discussed.The enantioconvergent alkyl–alkyl coupling involves two competitive catalytic cycles with nickel(0) and nickel(i) active catalysts, respectively. K3PO4 plays a crucial role to enable the hydride transfer from hydrosilane to nickel–bromine species. 相似文献
9.
We report the addition of M–H bonds (M = Al, Zn, Mg) to a Rh(iii) intermediate generated from the reductive elimination of triethylsilane from [Cp*Rh(H)2(SiEt3)2]. A series of new heterobimetallic complexes possessing Rh–M bonds have been isolated and characterised by a number of spectroscopic (1H, 29Si, 13C, 103Rh NMR, infrared, and X-ray diffraction) and computational techniques (NBO and QTAIM analysis). Experimental and computational data are consistent with cleavage of the M–H bond upon addition to rhodium with formation of new Rh–M and Rh–H bonds. Upon photolysis the Al analogue of this series undergoes a further elimination reaction producing triethylsilane and a highly unusual Rh2Al2H4 containing cluster proposed to contain an Al(i) bridging ligand. 相似文献
10.
Shaochuan Li Caiping Liu Qihui Chen Feilong Jiang Daqiang Yuan Qing-Fu Sun Maochun Hong 《Chemical science》2022,13(31):9016
Coordination hosts based on flexible ligands have received increasing attention due to their inherent adaptive cavities that often show induced-fit guest binding and catalysis like enzymes. Herein, we report the controlled self-assembly of a series of homo/heterometallic coordination hosts (Me4enPd)2n(ML)n [n = 2/3; M = Zn(ii)/Co(ii)/Ni(ii)/Cu(ii)/Pd(ii)/Ag(i); Me4en: N,N,N′,N′-tetramethylethylenediamine] with different shapes (tube/cage) from a flexible tetraazacyclododecane-based pyridinyl ligand (L) and cis-blocking Me4enPd(ii) units. While the Ag(i)-metalated ligand (AgL) gave rise to the formation of a (Me4enPd)4(ML)2-type cage, all other M(ii) ions led to isostructural (Me4enPd)6(ML)3-type tubular complexes. Structural transformations between cages and tubes could be realized through transmetalation of the ligand. The buffering effect on the ML panels endows the coordination tubes with remarkable acid–base resistance, which makes the (Me4enPd)6(ZnL)3 host an effective catalyst for the CO2 to CO32− conversion. Control experiments suggested that the integration of multiple active Zn(ii) sites on the tubular host and the perfect geometry match between CO32− and the cavity synergistically promoted such a conversion. Our results provide an important strategy for the design of adaptive coordination hosts to achieve efficient carbon fixation.A series of coordination hosts were prepared and their applications in CO2 fixation were studied. 相似文献
11.
Organocopper(ii) complexes are a rarity while organocopper(i) complexes are commonplace in chemical synthesis. In the course of building a strategy to generate organocopper(ii) species utilizing electrochemistry, a method to form compounds with CuII–C bonds was discovered, that demonstrated remarkably potent reactivity towards different functionalized alkenes under catalytic control. The role of the organocopper(ii) complex is to act as a source of masked radicals (in this case ˙CH2CN) that react with an alkene to generate the corresponding γ-halonitrile in good yields through atom transfer radical addition (ATRA) to various alkenes. The organocopper(ii) complexes can be continuously regenerated electrochemically for ATRA (eATRA), which proceeds at room temperature, under low Cu loadings (1–10 mol%) and with the possibility of Cu-catalyst recovery.Electrochemical generation of a novel organocopper(ii) complex offers a new way to carry out atom transfer radical addition to alkenes under mild conditions with high yields and low catalyst loadings. 相似文献
12.
A dinickel(0)–N2 complex, stabilized with a rigid acridane-based PNP pincer ligand, was studied for its ability to activate C(sp2)–H and C(sp2)–O bonds. Stabilized by a Ni–μ–N2–Na+ interaction, it activates C–H bonds of unfunctionalized arenes, affording nickel–aryl and nickel–hydride products. Concomitantly, two sodium cations get reduced to Na(0), which was identified and quantified by several methods. Our experimental results, including product analysis and kinetic measurements, strongly suggest that this C(sp2)–H activation does not follow the typical oxidative addition mechanism occurring at a low-valent single metal centre. Instead, via a bimolecular pathway, two powerfully reducing nickel ions cooperatively activate an arene C–H bond and concomitantly reduce two Lewis acidic alkali metals under ambient conditions. As a novel synthetic protocol, nickel(ii)–aryl species were directly synthesized from nickel(ii) precursors in benzene or toluene with excess Na under ambient conditions. Furthermore, when the dinickel(0)–N2 complex is accessed via reduction of the nickel(ii)–phenyl species, the resulting phenyl anion deprotonates a C–H bond of glyme or 15-crown-5 leading to C–O bond cleavage, which produces vinyl ether. The dinickel(0)–N2 species then cleaves the C(sp2)–O bond of vinyl ether to produce a nickel(ii)–vinyl complex. These results may provide a new strategy for the activation of C–H and C–O bonds mediated by a low valent nickel ion supported by a structurally rigidified ligand scaffold.A structurally rigidified nickel(0) complex was found to be capable of cleaving both C(sp2)–H and C(sp2)–O bonds. 相似文献
13.
Alexandre Abhervé Samuel Ma?as-Valero Miguel Clemente-León Eugenio Coronado 《Chemical science》2015,6(8):4665-4673
The syntheses, structures and magnetic properties of the coordination compounds of formula [FeIII(acac2-trien)][MnIICrIII(Cl2 An)3]·(CH3CN)2 (1), [FeIII(acac2-trien)][MnIICrIII(Br2An)3]·(CH3CN)2 (2) and [GaIII(acac2-trien)][MnIICrIII(Br2An)3]·(CH3CN)2 (3) are reported. They exhibit a 2D anionic network formed by Mn(ii) and Cr(iii) ions linked through anilate ligands, while the [FeIII(acac2-trien)]+ or [GaIII(acac2-trien)]+ charge-compensating cations are placed inside the hexagonal channels of the 2D network, instead of being inserted in the interlamellar spacing. Thus, these crystals are formed by hybrid layers assembled through van der Waals interactions. The magnetic properties indicate that these compounds behave as magnets exhibiting a long-range ferrimagnetic ordering at ca. 11 K, while the inserted Fe(iii) cations remain in the high-spin state. As for graphene, these layered materials can be exfoliated in atomically-thin layers with heights down to 2 nm by using the well-known Scotch tape method. Hence, this micromechanical procedure provides a suitable way to isolate ultrathin layers of this kind of graphene related magnetic materials. Interestingly, this method can also be successfully used to exfoliate the 2D anilate-based compound [FeIII(sal2-trien)][MnIICrIII(Cl2An)3]·solv (4), which exhibits the typical alternated cation/anion layered structure. This result shows that the micromechanical exfoliation method, which has been extensively used for exfoliating van der Waals layered solids, can also be useful for exfoliating layered coordination compounds, even when they are formed by ionic components. 相似文献
14.
Johnson Lui-Lui Tsai Taotao Zou Jia Liu Tianfeng Chen Anna On-Yee Chan Chen Yang Chun-Nam Lok Chi-Ming Che 《Chemical science》2015,6(7):3823-3830
Supramolecular interactions are of paramount importance in biology and chemistry, and can be used to develop new vehicles for drug delivery. Recently, there is a surge of interest on self-assembled functional supramolecular structures driven by intermolecular metal–metal interactions in cellular conditions. Herein we report a series of luminescent Pt(ii) complexes [Pt(C^N^Npyr)(CNR)]+ [HC^N^Npyr = 2-phenyl-6-(1H-pyrazol-3-yl)-pyridine)] containing pincer type ligands having pyrazole moieties. These Pt(ii) complexes exert potent cytotoxicity to a panel of cancer cell lines including primary bladder cancer cells and display strong phosphorescence that is highly sensitive to the local environment. The self-assembly of these complexes is significantly affected by pH of the solution medium. Based on TEM, SEM, ESI-MS, absorption and emission spectroscopy, and fluorescence microscopy together with cell based assays, [Pt(C^N^Npyr)(CNR)]+ complexes were observed to self-assemble into orange phosphorescent polymeric aggregates driven by intermolecular Pt(ii)–Pt(ii) and ligand–ligand interactions in a low-pH physiological medium. Importantly, the intracellular assembly and dis-assembly of [Pt(C^N^Npyr)(CNR)]+ are accompanied by change of emission color from orange to green. These [Pt(C^N^Npyr)(CNR)]+ complexes accumulated in the lysosomes of cancer cells, increased the lysosomal membrane permeability and induced cell death. One of these platinum(ii) complexes formed hydrogels which displayed pH-responsive and sustained release properties, leading to low-pH-stimulated and time-dependent cytotoxicity towards cancer cells. These hydrogels can function as vehicles to deliver anti-cancer agent cargo, such as the bioactive natural products studied in this work. 相似文献
15.
William J. Ramsay Jonathan A. Foster Katharine L. Moore Tanya K. Ronson Rapha?l J. Mirgalet David A. Jefferson Jonathan R. Nitschke 《Chemical science》2015,6(12):7326-7331
The incorporation of an N-heterocyclic carbene (NHC) moiety into a self-assembled MII4L6 cage framework required the NHC first to be metallated with gold(i). Bimetallic cages could then be constructed using zinc(ii) and cadmium(ii) templates, showing weak luminescence. The cages were destroyed by the addition of further gold(i) in the form of AuI(2,4,6-trimethoxybenzonitrile)2SbF6, which caused the reversibly-formed cages to disassemble and controllably release the AuI-NHC subcomponent into solution. This release in turn induced the growth of gold nanoparticles. The rate of dianiline release could be tuned by capsule design or through the addition of chemical stimuli, with different release profiles giving rise to different nanoparticle morphologies. 相似文献
16.
Jing Su Thibault Cheisson Alex McSkimming Conrad A. P. Goodwin Ida
M. DiMucci Thomas Albrecht-Schnzart Brian L. Scott Enrique R. Batista Andrew J. Gaunt Stosh A. Kozimor Ping Yang Eric J. Schelter 《Chemical science》2021,12(40):13343
There is significant interest in ligands that can stabilize actinide ions in oxidation states that can be exploited to chemically differentiate 5f and 4f elements. Applications range from developing large-scale actinide separation strategies for nuclear industry processing to carrying out analytical studies that support environmental monitoring and remediation efforts. Here, we report syntheses and characterization of Np(iv), Pu(iv) and Am(iii) complexes with N-tert-butyl-N-(pyridin-2-yl)hydroxylaminato, [2-(tBuNO)py]−(interchangeable hereafter with [(tBuNO)py]−), a ligand which was previously found to impart remarkable stability to cerium in the +4 oxidation state. An[(tBuNO)py]4 (An = Pu, 1; Np, 2) have been synthesized, characterized by X-ray diffraction, X-ray absorption, 1H NMR and UV-vis-NIR spectroscopies, and cyclic voltammetry, along with computational modeling and analysis. In the case of Pu, oxidation of Pu(iii) to Pu(iv) was observed upon complexation with the [(tBuNO)py]− ligand. The Pu complex 1 and Np complex 2 were also isolated directly from Pu(iv) and Np(iv) precursors. Electrochemical measurements indicate that a Pu(iii) species can be accessed upon one-electron reduction of 1 with a large negative reduction potential (E1/2 = −2.26 V vs. Fc+/0). Applying oxidation potentials to 1 and 2 resulted in ligand-centered electron transfer reactions, which is different from the previously reported redox chemistry of UIV[(tBuNO)py]4 that revealed a stable U(v) product. Treatment of an anhydrous Am(iii) precursor with the [(tBuNO)py]− ligand did not result in oxidation to Am(iv). Instead, the dimeric complex [AmIII(μ2-(tBuNO)py)((tBuNO)py)2]2 (3) was isolated. Complex 3 is a rare example of a structurally characterized non-aqueous Am-containing molecular complex prepared using inert atmosphere techniques. Predicted redox potentials from density functional theory calculations show a trivalent accessibility trend of U(iii) < Np(iii) < Pu(iii) and that the higher oxidation states of actinides (i.e., +5 for Np and Pu and +4 for Am) are not stabilized by [2-(tBuNO)py]−, in good agreement with experimental observations.The coordination modes and electronic properties of a strongly coordinating hydroxylaminato ligand with Np, Pu and Am were investigated.Complexes were characterized by a range of experimental and computational techniques. 相似文献
17.
S. Fedrigo T. L. Haslett M. Moskovits 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,40(1):99-101
Metal complexes produced by depositing size selected Fe and Ag cluster cations in N2 and O2 matrices respectively are studied by infrared spectroscopy. Unknown species such as Fe(N2)x, Fe3 (N2)x and Ag3(O2)x are observed. The IR spectra of Ag+, Ag 2 + and Ag 9 + in excess O2 indicate that no complexes involving molecular oxygen are formed. However, the strong silver cluster UV-visible absorptions detected in Ar matrices disappear in the oxygen matrices, suggesting that silver-oxygen complexes are formed with dissociated oxygen. 相似文献
18.
Jiahui Shen Victor Terskikh Jochem Struppe Alia Hassan Martine Monette Ivan Hung Zhehong Gan Andreas Brinkmann Gang Wu 《Chemical science》2022,13(9):2591
We report synthesis and solid-state 17O NMR characterization of α-d-glucose for which all six oxygen atoms are site-specifically 17O-labeled. Solid-state 17O NMR spectra were recorded for α-d-glucose/NaCl/H2O (2/1/1) cocrystals under static and magic-angle-spinning (MAS) conditions at five moderate, high, and ultrahigh magnetic fields: 14.1, 16.4, 18.8, 21.1, and 35.2 T. Complete 17O chemical shift (CS) and quadrupolar coupling (QC) tensors were determined for each of the six oxygen-containing functional groups in α-d-glucose. Paramagnetic Cu(ii) doping was found to significantly shorten the spin–lattice relaxation times for both 1H and 17O nuclei in these compounds. A combination of the paramagnetic Cu(ii) doping, new CPMAS CryoProbe technology, and apodization weighted sampling led to a sensitivity boost for solid-state 17O NMR by a factor of 6–8, which made it possible to acquire high-quality 2D 17O multiple-quantum (MQ) MAS spectra for carbohydrate compounds. The unprecedented spectral resolution offered by 2D 17O MQMAS spectra permitted detection of a key structural difference for a single hydrogen bond between two types of crystallographically distinct α-d-glucose molecules. This work represents the first case where all oxygen-containing functional groups in a carbohydrate molecule are site-specifically 17O-labeled and fully characterized by solid-state 17O NMR. Gauge Including Projector Augmented Waves (GIPAW) DFT calculations were performed to aid 17O and 13C NMR signal assignments for a complex crystal structure where there are six crystallographically distinct α-d-glucose molecules in the asymmetric unit.We report the first “total synthesis” of 17O-labeled d-glucose and its solid-state 17O NMR characterization with unprecedented sensitivity and resolution. 相似文献
19.
Takao M. Kojima Nobuo Kobayashi Yozaburo Kaneko 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1992,23(2):181-185
The formation of cluster ions when hydrogen molecular ions H 2 + and H 3 + are injected into a drift tube filled with helium gas at 4.4 K has been investigated. When H 2 + ions are injected, cluster ions HHe x + (x≦14) are produced. No production of H2He x + ions is observed. When H 3 + ions are injected, cluster ions HHe x + (x≦14) are produced as well as H3He x + (x≦13), and very small signals corresponding to H2He x + (3≦x≦10) are observed. Information on the stability of HHe x + and H3He x + is derived from the drift field dependence of the cluster size distributions. The cluster sizex=13 is found to be a magic number for HHe x + , and for H3He x + ,x=10 and 11. 相似文献
20.
David Pertuit Anne-Claire Mitaine-Offer Tomofumi Miyamoto Chiaki Tanaka Christine Belloir Loïc Briand Marie-Aleth Lacaille-Dubois 《Molecules (Basel, Switzerland)》2021,26(22)
Four oleanane-type glycosides were isolated from a horticultural cultivar “Green Elf” of the endemic Pittosporum tenuifolium (Pittosporaceae) from New Zealand: three acylated barringtogenol C glycosides from the leaves, with two previously undescribed 3-O-β-d-glucopyranosyl-(1→2)-[α-l-arabinopyranosyl-(1→3)]-β-d-glucuronopyranosyl-21-O-angeloyl-28-O-acetylbarringtogenol C, 3-O-β-d-galactopyranosyl-(1→2)-[α-l-arabinopyranosyl-(1→3)]-β-d-glucuronopyranosyl-21-O-angeloyl-28-O-acetylbarringtogenol C, and the known 3-O-β-d-glucopyranosyl-(1→2)-[α-l-arabinopyranosyl-(1→3)]-β-d-glucuronopyranosyl-21-O-angeloyl-28-O-acetylbarringtogenol C (Eryngioside L). From the roots, the known 3-O-β-d-glucopyranosyl-(1→2)-β-d-galactopyranosyl-(1→2)-β-d-glucuronopyranosyloleanolic acid (Sandrosaponin X) was identified. Their structures were elucidated by spectroscopic methods including 1D- and 2D-NMR experiments and mass spectrometry (ESI-MS). According to their structural similarities with gymnemic acids, the inhibitory activities on the sweet taste TAS1R2/TAS1R3 receptor of an aqueous ethanolic extract of the leaves and roots, a crude saponin mixture, 3-O-β-d-glucopyranosyl-(1→2)-[α-l-arabinopyranosyl-(1→3)]-β-d-glucuronopyranosyl-21-O-angeloyl-28-O-acetylbarringtogenol C, and Eryngioside L were evaluated. 相似文献